【摘要】：本論文以苯并咪唑并苯并異喹啉酮為熒光核,在12位羧基上引入四種不同的識別基團(tuán),合成了四種熒光探針:苯并咪唑并苯并異喹啉酮-12-羧酸(L1),N-(4-(2-肟基-2-乙酸乙酯)噻唑-2)苯并咪唑并苯并異喹啉酮-12-羧酸酰胺(L2),N-(戊二酸-2)-苯并咪唑并苯并異喹啉酮-12-羧酸酰胺(L3)和N-(丁二酸-2)-苯并咪唑并苯并異喹啉酮-12-羧酸酰胺(L4)。以上四種苯并咪唑并苯并異喹啉酮衍生物以及它們的中間體的化學(xué)結(jié)構(gòu)均通過了1H NMR(氫譜)、13C NMR(碳譜)、MS(質(zhì)譜)以及FTIR(紅外)等表征手段的驗證,并且用紫外分光光度儀和熒光分光光度儀對其光學(xué)性質(zhì)進(jìn)行了更深入的研究。研究發(fā)現(xiàn),以上四種以苯并咪唑并苯并異喹啉酮為熒光核的探針對不同的金屬離子表現(xiàn)出了不同的響應(yīng)特性:探針L1在乙腈/水(v/v=1:1,pH=7.2)的緩沖體系中對Hg2+表現(xiàn)出高度的選擇性,是“打開”型熒光探針。通過Hg2+與陰離子PPi的多次相互滴加,獲知L1對Hg2+的檢測是可逆的。而且在不同pH的溶液中,L1的熒光強(qiáng)度有很大的變化。根據(jù)熒光測試結(jié)果,提出在酸性、中性及堿性溶液中L1分子以兩種不同的形式存在,分別為L1和L1-。L1狀態(tài)時形成一個分子內(nèi)氫鍵抑制了PET過程的進(jìn)行,從而顯示強(qiáng)熒光。去質(zhì)子化發(fā)生后,L1-中的PET過程恢復(fù),熒光淬滅。并得到了DFT/TDDFT理論計算的驗證。工作曲線顯示探針L1與Hg2+之間的絡(luò)合比為1:1。探針L2分子中去甲基氨噻肟酸乙酯基團(tuán)的存在使其在乙腈/水(v/v=9:1,pH=7.4)的緩沖體系中,對Fe~(3+)表現(xiàn)出高選擇性與高靈敏度,不受其他金屬離子的干擾,體現(xiàn)為熒光增強(qiáng)的響應(yīng)。檢測極限為9×10-8 M。在一定波長的激發(fā)下,L2的熒光顏色由淺綠色變成亮綠色。質(zhì)譜滴定證明L2與Fe~(3+)之間以1:1絡(luò)合。探針L3在純水(pH=7.4)緩沖體系中,對Fe~(3+)與Al~(3+)表現(xiàn)出不同程度的熒光淬滅。L3分子中兩個羧基的存在使其在酸性、中性及弱堿性、強(qiáng)堿性溶液中,熒光強(qiáng)度差別很大,而且在弱堿性溶液中熒光最強(qiáng)。通過理論計算,L3對pH的熒光響應(yīng)機(jī)理也得到了驗證。工作曲線顯示,L3與Fe~(3+)或Al~(3+)之間均為1:1絡(luò)合。探針L4與L3在結(jié)構(gòu)上很相似,因此,對Fe~(3+)和Al~(3+)的響應(yīng)結(jié)果也極為相似。不同之處在于,L4的熒光強(qiáng)度弱于L3的熒光強(qiáng)度。
[Abstract]:In this paper, four fluorescent probes, benzimidazole-benzisoquinolinone (L1), were synthesized by introducing four different recognition groups into 12 carboxyl groups, using benzimidazole benzo isoquinolinone as fluorescence nucleus. N- (4- (2-oximo-2-ethyl acetate) thiazole-2) benzimidazole benzisoquinolone-12-carboxylic acid amide (L2), N- (glutaric acid-2) -benzimidazolidazolone-12-carboxylic acid amide (L3) and N- (succinate-2) -benzimidazolinone benzisoquinolone-12-carboxylic acid amide (L4). The chemical structures of the four benzimidazole-benzo-isoquinolinone derivatives and their intermediates were confirmed by 1H NMR, 13C NMR (carbon spectrum), MS (mass spectrometry) and FTIR (infrared). The optical properties were studied by ultraviolet spectrophotometer and fluorescence spectrophotometer. It was found that the four probes with benzimidazolazole-benzo-isoquinolinone as fluorescence nuclei showed different response characteristics to different metal ions: the probe L1 was found to be in acetonitrile / water (v / v = 1: 1). PH=7.2) has a high selectivity for Hg2 in the buffer system and is a "open" fluorescent probe. By adding Hg2 and anionic PPi to each other for several times, it was found that the detection of L1 for Hg2 was reversible. Moreover, the fluorescence intensity of L1 varies greatly in different pH solutions. According to the results of fluorescence measurement, it is suggested that L1 molecules exist in two different forms in acidic, neutral and alkaline solutions. The formation of an intramolecular hydrogen bond in the states of L1 and L1-.L1 respectively inhibits the progress of the PET process, thus showing strong fluorescence. After deprotonation, the PET process in L 1-recovered and fluorescence quenching occurred. The calculation of DFT/TDDFT theory is verified. The working curve shows that the complexation ratio between probe L1 and Hg2 is 1: 1. The presence of ethyl demethylaminotaxime group in the probe L2 makes it exhibit high selectivity and high sensitivity to Fe~ (3) in the buffer system of acetonitrile / water (v / v 9: 1), and is not interfered with by other metal ions. Reflected in the fluorescence enhancement of the response. The detection limit is 9 脳 10 ~ (-8) M. Under the excitation of a certain wavelength, the fluorescence color of L 2 changed from light green to bright green. Mass spectrometric titration showed that L _ 2 complexed with Fe~ (3) at 1:1. The fluorescence quenching of Fe~ (3) and Al~ (3) in the buffer system of pure water (pH=7.4) showed that the probe L3 had two carboxyl groups in the solution of acid, neutral and weak alkalinity and strong alkalinity. The fluorescence intensity varies greatly, and the fluorescence is strongest in weak alkaline solution. The fluorescence response mechanism of L 3 to pH was also verified by theoretical calculation. The working curve showed that the complex between L 3 and Fe~ (3) or Al~ (3) was 1:1. The structure of probe L4 is similar to that of L3, so the response to Fe~ (3) and Al~ (3) is very similar. The difference is that the fluorescence intensity of L 4 is weaker than that of L 3.
【學(xué)位授予單位】：濟(jì)南大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O626;O657.3

【參考文獻(xiàn)】

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1 李輝;董毅;郝志云;楊新周;朱以常;;萘酰亞胺類熒光分子探針的研究進(jìn)展[J];化學(xué)研究;2014年03期

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本文編號：2400574